全文获取类型
收费全文 | 256260篇 |
免费 | 3744篇 |
国内免费 | 1365篇 |
专业分类
化学 | 141860篇 |
晶体学 | 3410篇 |
力学 | 9801篇 |
综合类 | 63篇 |
数学 | 30484篇 |
物理学 | 75751篇 |
出版年
2020年 | 2178篇 |
2019年 | 2233篇 |
2018年 | 2935篇 |
2017年 | 2982篇 |
2016年 | 4585篇 |
2015年 | 3154篇 |
2014年 | 4358篇 |
2013年 | 10622篇 |
2012年 | 9256篇 |
2011年 | 11128篇 |
2010年 | 7756篇 |
2009年 | 7376篇 |
2008年 | 10389篇 |
2007年 | 10392篇 |
2006年 | 9817篇 |
2005年 | 8981篇 |
2004年 | 7980篇 |
2003年 | 6950篇 |
2002年 | 6791篇 |
2001年 | 7410篇 |
2000年 | 5655篇 |
1999年 | 4083篇 |
1998年 | 3400篇 |
1997年 | 3371篇 |
1996年 | 3472篇 |
1995年 | 3050篇 |
1994年 | 3168篇 |
1993年 | 3026篇 |
1992年 | 3324篇 |
1991年 | 3232篇 |
1990年 | 3039篇 |
1989年 | 2933篇 |
1988年 | 2850篇 |
1987年 | 2807篇 |
1986年 | 2794篇 |
1985年 | 3751篇 |
1984年 | 3792篇 |
1983年 | 3163篇 |
1982年 | 3434篇 |
1981年 | 3191篇 |
1980年 | 2969篇 |
1979年 | 3153篇 |
1978年 | 3337篇 |
1977年 | 3367篇 |
1976年 | 3376篇 |
1975年 | 3108篇 |
1974年 | 3203篇 |
1973年 | 3215篇 |
1972年 | 2459篇 |
1971年 | 1997篇 |
排序方式: 共有10000条查询结果,搜索用时 14 毫秒
971.
L. P. Blanchard K. T. Dinh J. Moinard F. Tahiani 《Journal of polymer science. Part A, Polymer chemistry》1972,10(5):1353-1362
Anionic polymerizations of 1,2-butylene oxide were carried out in vacuum-sealed dilatometers in the range of 30–60°C. Potassium terbutoxide and dimsyl sodium were used as initiators; dimethyl sulfoxide (DMSO) and mixtures of DMSO with tetrahydrofuran were solvents. The polymer products were analyzed by gel permeation chromatography and infrared spectroscopy. The object of the investigation was to obtain information on the mechanism of the reaction and to elucidate some of its kinetic aspects. It has been shown that the polymerizations occur by two different processes, depending on the choice of experimental conditions. One of the processes involves free ions and ion-pairs, the other, ion-pairs alone. In the first case, where dimethyl sulfoxide is used as solvent, the order of the reaction with respect to the initiator concentration far exceeds unity (~1.8), while in the second case, involving mixed solvents, the order of the reaction, for all practical purposes, is one. 相似文献
972.
K. Bürner 《Analytical and bioanalytical chemistry》1968,243(1):68-79
The ATR-method is qualified for measuring aqueous solutions if the multiplereflection technique is used in such a way that strong water absorptions do not cover a large part of the information on the spectrum. The single-reflection technique is mainly suitable for solutions of 2-molar and higher concentrations. Organic acids, phenols, amides, saccharides and anorganic compounds had been measured. A practical example proved that there is the possibility of also taking quantitative measurements with the ATR-method. 相似文献
973.
Zusammenfassung Die derivatographische Methode wurde weiterentwickelt. Mit Hilfe einer neuen Einrichtung kann man die Temperatur, die Gewichtsänderung und die Dilatation der Probe sowie auch die Geschwindigkeit der Enthalpie- und Gewichtsänderungen und die Geschwindigkeit der Dilatation messen. Die Vorteile der Einrichtung wurden an einigen praktischen Beispielen erläutert.
Bei der Ausführung der Versuche waren uns FrauM. Csonka und FrauE. Borsay behilflich, wofür wir ihnen auch an dieser Stelle danken. 相似文献
Summary The derivatographic method was further developed. With the aid of a new apparatus it is possible to measure the temperature, the change in weight and the dilatation of the sample, as well as the velocity of the changes; in enthalpy and weight and the velocity of the dilatation. The advantages of the apparatus were demonstrated by means of several practical examples.
Résumé On a élargi le domaine des méthodes dérivatographiques. A l'aide d'un nouveau dispositif, on peut mesurer la température, la variation de poids et la dilatation de l'échantillon, ainsi que la vitesse des changements d'enthalpie et de poids, et aussi la vitesse de la dilatation. On a montré les avantages de ce dispositif sur un certain nombre d'exemples pratiques.
Bei der Ausführung der Versuche waren uns FrauM. Csonka und FrauE. Borsay behilflich, wofür wir ihnen auch an dieser Stelle danken. 相似文献
974.
Zusammenfassung Die dielektrischen Verluste diphenylmethylierter und chlorierter Poly?thylene k?nnen in Einzelheiten quantitativ richtig dargestellt
werden, wenn man annimmt, da\ das Copolymerensystem pseudo-eutektischen Charakter hat. Die dipoltragenden Gruppen (CHCl bzw.
Diphenylmethan-CH) werden offenbar nicht in die Kristalle, wohl aber in die longitudinalen Grenzschichten eingebaut. Dasα-Maximum ist den Dipolen in der Grenzschicht, dasΒ-Maximum den Dipolen im Innern der amorphen Anteile zuzuordnen. Die Temperaturlage und die Fl?che unter diesen Verlustmaxima
h?ngen in bestimmter Weise von der mittleren Kristalldicke ab. Eine klare Zuordnung von Strukturdaten und Daten aus dem Relaxationsspektrum
ist durch eine erweiterte quantitative Analyse der dielektrischen Me\ergebnisse m?glich.
Es sind dann nicht nur die Temperaturlage desα- und desΒ-Maximums, sondern auch deren relative Fl?chen?nderungen in übereinstimmung mit dem Experiment berechenbar. Dies ist eine
scharfe quantitative Konsistenzprüfung des erweiterten Stuktur-modells, wonach die Kristalle longitudinale Grenzschichten
von definierter mittlerer Dicke besitzen sollen.
Mit Hilfe der Zwei-Drittel-Regel kann man bei Kenntnis der wahren Konzentration der Comonomereneinheiten in den amorphen Zwischenbereichen
kristallisierter Proben die Temperaturlage der glasigen Erstarrung abh?ngig von der Gesamtkonzentration sehr gut angeben.
Die Lage der Glastemperatur sollte hiernach im Vergleich zur Glastemperatur des ‚'unendlich gro\en“ amorphen Systems derselben
Konzentration durch die Kristallisation nicht ver?ndert werden.
Wir danken der Deutschen Forschungsge-meinschaft für die gro\zügige Bereitstellung von Sach- und Personalmitteln. 相似文献
975.
Wei Q Nieuwenhuyzen M Meunier F Hardacre C James SL 《Dalton transactions (Cambridge, England : 2003)》2004,(12):1807-1811
The metal-organic framework [Co(INA)(2)]x0.5EtOH (INA = isonicotinate, NC(5)H(4)-4-CO(2)(-)), was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between 'open' and 'closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 A at the narrowest point to 4.9 by 5.3 A at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 A) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)] shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)]x0.5Pr(n)OHxH(2)O, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for than with or, suggesting that they may have disordered structures similar to. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material. 相似文献
976.
Up to 100 microg of sample can be collected from gold or silver alloys by rubbing the specimen with the ground hemispherical tip of a 4-mm Pyrex glass rod. Gold alloys are then dissolved in potassium cyanide solution containing hydrogen peroxide; silver alloys are exposed to vapours of nitric acid. Procedures for transfer, ring oven separation and identification of alloy constituents in the sample solutions are described. 相似文献
977.
A. L. Podkorytov S. R. Kudakaeva E. V. Sokolova S. A. Shtin D. N. Ashikhmin 《Russian Journal of Inorganic Chemistry》2006,51(1):46-50
The main features of the synthesis of (Pb1-x
Srx)2Nb2O7 and (Pb1-x
Bax)2Nb2O7 pyrochlore solid solutions were determined using isothermal thermogravimetry in tandem with formal-kinetic analysis. The
stability and electron-transport properties of the triple niobates were studied, which allowed us to test them as electrode-active
materials for membranes in ion-selective electrodes (ISEs). 相似文献
978.
M. Domínguez-Pérez J. Jiménez de Llano L. Segade C. Franjo O. Cabeza 《Journal of Thermal Analysis and Calorimetry》2005,79(2):289-293
Summary This paper reports excess molar enthalpies of the binary systems hexane+ethyl benzene, hexane+o-xylene, hexane+m-xylene and hexane+p-xylene at 298.15 K and atmospheric pressure, over the whole composition range. The data was measured directly using a Calvet microcalorimeter. The excess magnitude was correlated to a Redlich-Kister type equation for each mixture. Also, we will discuss the results for the four mixtures studied here and by comparison with the same binary systems but containing propyl propanoate as first component. Finally, we will correlate our results with the Nitta-Chao and the three UNIFAC theoretical approximations. 相似文献
979.
Electron deficient 1,2-diacylcyclopropenes represent synthetic equivalent for both acylcarbenes and vinylcarbenes; in their cycloreaction with ynamines aminofuranes and/or aminocyclopentadienes are formed. 相似文献
980.
The optimization of a rather complex wet chemical analysis method, such as the measurement of Kjeldahl nitrogen or total phosphorus with the Technicon AutoAnalyzer, is extremely tedious when purely empirical approaches are used. A mathematical model of the different stages of the measuring method (digestion, neutralization and color reaction) is described. The system can then be optimized for maximum measuring sensitivity. Optimization is done by solving numerically the non-linear optimization problem with constraints. The starting values for the optimization algorithm were found by varying these values systematically within the tolerated range, with checks that none of the constraints were violated. The theoretical results predict an increase in sensitivity by a factor of 15 compared to the method used previously. In practice, the sensitivity was increased by a factor of 10 for the total phosphorus method. For the simultaneous low-level determinations of Kjeldahl nitrogen and total phosphorus some problems of stability remain. 相似文献